JP2003525286A5 - - Google Patents

Description

[0015]
Z are each, independently of one another, a single _{bond, -CH 2 -CH 2 -, -} CF 2 -CF 2 -, - CF 2 -CH 2 -, - CH 2 -CF 2 -, - CF = CF- , —CH═CH—, —C≡C—, —CO—O—, —O—CO—, —CF ₂ —O— or —O—CF ₂ —,
—S— (CR ² R ³ ) _n —S— is a bridge composed of two sulfur atoms connected by a carbon chain having 2 or 3 carbon atoms, and one hydrocarbon bridge or Optionally having two or more substituents R ² and R ³ , in particular an alkyl or alkylene group in which the R ² and R ³ groups may form a cycloalkyl group or an aryl group with one another. Yes,
m is an integer of 0-6,
n is 2 or 3, and Y ⁻ is all desirable anions.

[0018]
The compound containing at least one hydroxyl group, preferably optionally substituted, in particular polar groups, preferably -F, -Cl, -CN, -NCS, may be substituted with -OCF ₃ or -OCH ₂ F Phenol, or an alkyl, cycloalkyl, or 4-phenyl group that may be substituted with an alkyl, cycloalkyl, or phenyl group in order, and a hydrogen atom is substituted with a fluorine or chlorine atom. at best, and in any _{case, -CH 2 -CH 2 -, -} CF 2 -CF 2 -, - CF 2 -CH 2 -, - CH 2 -CF 2 -, - CF = CF -, - CH═CH—, —C≡C—, —COO—, —O—CO—, —O—CF ₂ —, —CH ₂ —O—, —O—CH ₂ — or —CF ₂ —O— group is Exist between these groups It may be.

４−（４’−ペンチルシクロヘキシル）シクロヘキサンカルボン酸１０ｇを、１，３−プロパンジチオール３．６ｍｌと混合し、および冷浴で冷却した。トリフルオロメタンスルホン酸７．９ｍｌを加えた。添加が完了した後、混合物を１２０℃に加熱し、および３０分間攪拌した。反応混合物を熱浴から取り出し、１０ｍｌのアセトニトリルに溶解した。溶液を、５０ｍｌの氷で冷却したエーテルに注ぎ、および無色の小板を沈殿させた。混合物を−２０℃で別に２時間冷却し、およびその後、窒素下で吸引濾過した。真空で乾燥し、無色の小板を得た。 収率：１０．９ｇ（理論に対し６０．２％）
^１３ＣＮＭＲ（ＣＤＣｌ_３、３０３Ｋ）：δ_{カルヘ゛ニウム}＝２０３．５ｐｐｍ[0028]
Example 2
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10 g of 4- (4′-pentylcyclohexyl) cyclohexanecarboxylic acid was mixed with 3.6 ml of 1,3-propanedithiol and cooled in a cold bath. 7.9 ml of trifluoromethanesulfonic acid was added. After the addition was complete, the mixture was heated to 120 ° C. and stirred for 30 minutes. The reaction mixture was removed from the heat bath and dissolved in 10 ml acetonitrile. The solution was poured into 50 ml ice-cold ether and a colorless platelet was precipitated. The mixture was cooled at −20 ° C. for another 2 hours and then filtered with suction under nitrogen. Drying in vacuo gave a colorless platelet. Yield: 10.9 g (60.2% of theory)
¹³ C NMR (CDCl ₃ , 303K): δ _carbonium = 203.5 ppm

４−ペンチルシクロヘキサンカルボン酸１９９ｇを、１００ｍｌの１，３−プロパンジチオールと混合し、および冷浴で冷却した。２６３ｍｌのトリフルオロメタンスルホン酸を一滴ずつ加えた。添加が完了した後、反応混合物を１２０℃で１時間加熱した。反応混合物をおよそ７０℃まで冷却し、およびその後５００ｍｌの氷で冷却したジブチルエーテル上に注ぎ、および溶液を一晩、−２０℃で冷却した。沈殿した結晶を、吸引濾過し、エーテルで洗浄しおよび真空で乾燥した。
収率：９２ｇ（理論に対し２１．９％）[0030]
Example 4
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199 g of 4-pentylcyclohexanecarboxylic acid was mixed with 100 ml of 1,3-propanedithiol and cooled in a cold bath. 263 ml of trifluoromethanesulfonic acid was added dropwise. After the addition was complete, the reaction mixture was heated at 120 ° C. for 1 hour. The reaction mixture was cooled to approximately 70 ° C. and then poured onto 500 ml ice-cold dibutyl ether and the solution was cooled overnight at −20 ° C. The precipitated crystals were filtered off with suction, washed with ether and dried in vacuo.
Yield: 92 g (21.9% of theory)

[0037]
Example 8
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Claims (2)

Oxidizing agent is a compound which releases halonium equivalents, and in particular, dimethyl dibromohydantoin, N- bromosuccinimide, N- iodosuccinimide, _{bromine, SO 2 Cl 2, SO 2} ClF, nitrosonium and nitronium salts and chloramine T The method according to claim 1, wherein the method is selected from the group consisting of: Formula I

Where R ¹ ,

_{^{, -S- (CR 2 R 3)}} n -S-, Y -, m and n are as defined in claim 2,
A bis (alkylthio) carbenium salt represented by: